EP0008849B2 - Process for preparing acrylonitrile polymer fiber - Google Patents

Process for preparing acrylonitrile polymer fiber Download PDF

Info

Publication number
EP0008849B2
EP0008849B2 EP79301263A EP79301263A EP0008849B2 EP 0008849 B2 EP0008849 B2 EP 0008849B2 EP 79301263 A EP79301263 A EP 79301263A EP 79301263 A EP79301263 A EP 79301263A EP 0008849 B2 EP0008849 B2 EP 0008849B2
Authority
EP
European Patent Office
Prior art keywords
fiber
water
polymer
molecular weight
acrylonitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79301263A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0008849B1 (en
EP0008849A1 (en
Inventor
Harold Porosoff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25471087&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0008849(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to AT79301263T priority Critical patent/ATE928T1/de
Publication of EP0008849A1 publication Critical patent/EP0008849A1/en
Publication of EP0008849B1 publication Critical patent/EP0008849B1/en
Application granted granted Critical
Publication of EP0008849B2 publication Critical patent/EP0008849B2/en
Expired legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/088Cooling filaments, threads or the like, leaving the spinnerettes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • This application relates to a process for preparing acrylonitrile polymer fibre.
  • a preferred procedure for conducting this process is to spin the fusion melt directly into a steam-pressurized solidification zone which controls the rate of release of water from the nascent extru-- date to prevent deformation thereof as it leaves the spinnerette and enables a high degree of filament to be obtained.
  • Stretching of the extruded fiber is preferably carried out in the solidification zone.
  • the process of the present invention is characterized by the use of an acrylonitrile polymer which is a copolymer, containing at least 1 mol percent of comonomer, and which has a number average molecular weight of at least 6,000 but less than 15,000, and by conducting stretching of the extrudate in the steam-pressurized solidification zone in two stages so as to provide a total stretch ratio of at least 25, with the first stage of stretching being at a stretch ratio less than that of the second stage.
  • an acrylonitrile polymer which is a copolymer, containing at least 1 mol percent of comonomer, and which has a number average molecular weight of at least 6,000 but less than 15,000
  • a preferred processing step is that of drying the stretched extrudate under coditions of temperature and humidity to remove water therefrom while avoiding formation of a separate water phase therein. After such drying, it is generally preferred to conduct steam-relaxation on the dried extrudate under conditions which provide shrinkage thereof to the extent of 15-40%.
  • the process of the present invention unexpectedly provides acrylonitrile polymer fiber of useful physical properties for many applications in spite of the fact that it employs polymers of number average molecular weight values that are reported to be too low to provide fiber of any value.
  • the fiber obtained by the process of the present invention has desirable physical properties that render it useful in many industrial applications as well as for textile purposes depending upon processing stems conducted thereon.
  • the fiber obtained by the process of the present invention has physical properties that are equivalent to many of the current acrylonitrile polymer fibers commercially offered and, therefore are useful in those same applications that the commercial acrylonitrile polymer fibers are employed.
  • the fiber obtained by the process of the present invention is useful in textile, carpet, paper and other industrial applications.
  • the composition of the fiber-forming acrylonitrile polymer used in the present invention will be the same as any of those previously known fiber-forming acrylonitrile polymers but the acrylonitrile polymer used in the present invention will differ therefrom in number average molecular weight.
  • the acrylonitrile polymer used in the present invention will have a number average molecular weight of at least 6,000 but less than 15,000, preferably 7,500 to 14,500.
  • polymerization should be conducted so as to provide the proper number average molecular weight in accordance with conventional procedures.
  • the number average molecular weight values (M n ) reported in the present application were determined by gel permeation chromatography using a Waters Gel Permeation Chromatograph, cross-linked polystyrene gel column packing and dimethyl formamide-0.1 molar lithium bromide solvent.
  • the chromatograph was calibrated using a set of four acrylonitrile polymers for which Nf, and the weight average molecular weight (M n ) has been determiend by membrane osmometry and light scattering measurements, respectively.
  • the GPC calibration constants were determined by adjusting them to get the best fit between M n and M w values and values calculated from the chromatograms of polydisperse samples.
  • Useful polymers for the process in accordance with the present invention are copolymers of acrylonitrile and one or more monomers copolymerizable therewith. Such polymers will contain at least 1 mol percent of comonomer, preferably at least 3 mol percent thereof. The copolymer will contain at least about 50 mol percent of acrylonitrile preferably at least 70 mol percent thereof.
  • a suitable acrylonitrile polymer Once a suitable acrylonitrile polymer has been selected, it is necessary to provide a homogeneous fusion melt of the polymer and water at a temperature above the boiling point of water at atmospheric pressure and at a superatmospheric pressure sufficient to maintain water and polymer as a homogeneous fusion melt.
  • the particular temperatures and pressures useful will vary widely depending upon polymer composition but can readily be determined following prior art teachings, which also teach the proper proportions of polymer and water necessary to provide a homogeneous fusion melt.
  • the homogeneous fusion melt After the homogeneous fusion melt is provided, it is spun through a spinnerette directly into a steam-pressurized solidification zone.
  • the steam-pressurized solidification zone is maintained under conditions such that the rate of release of water from the nascent extrudate is controlled so as to prevent deformation of the extrudate as it emerges from the spinnerette.
  • the extrudate After the extrudate exits from the solidification zone, it may be further processed in accordance with conventional procedures.
  • Such drying provides fiber of improved transparency and improved dye intensity.
  • the acrylonitrile polymer fiber provided by the present invention is typical of acrylonitrile polymer fibers in general and differs therefrom essentially only in the number average molecular weight of the fiber-forming polymer, the present invention employing a lower number average molecular weight value.
  • homopolymers of acrylonitrile are contemplated in the prior art as fiber-forming polymers, the present invention requires at least 1 mol percent of comonomer in the polymer composition to provide processability.
  • the present invention in spite of its use of low molecular weight fiber-forming polymers, provides acrylonitrile polymer fiber that has physical property values well within the range of typical acrylic fiber properties and in many cases exceeds these values.
  • An acrylonitrile polymer containing 89.3% acrylonitrile and 10.7% methyl methacrylate was prepared according to conventional suspensions procedures to provide a polymer having a - number average molecular weight of 20,500.
  • the isolated polymer cake was dried to obtain a powder containing 18.1% water.
  • the polymer-water mixture was heated under autogeneous pressure in a screw extruder to provide a fusion melt at 180°C.
  • the resulting melt was spun through a spinnerette directly into a steam-pressurized solidification zone maintained at 22 pounds per square inch gauge pressure (1.52 bar).
  • the nascent extrudate was subjected to two stages of stretching while in the solidification zone, a first stage at a stretch ratio of 2.3 and a second stage at a stretch ratio of 10 to provide a total stretch ratio of 23.
  • the resulting 3.7 denier per filament tow was relaxed in steam at 124°C to provide fiber of 5.3 denier per filament (d/f). Properties of the relaxed fiber are given in Table I which follows.
  • Comparative Example B The procedure of Comparative Example B was repeated in every material detail except that the polymer had a number average molecular weight of 13,200, the fusion melt was processed at 195°C, the solidification zone was maintained at 18 psig (1.24 bar), the first stage stretch was at a stretch ratio of 3.3 and the second stage stretch was at a stretch ratio of 13.8 to provide a total stretch ratio of 44, and the 2.3 d/f fiber was relaxed in steam at 124°C to provide a 3.25 d/f fiber. Properties of the fiber are also given in Table I.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 89.7% acrylonitrile and 10.3% methyl methacrylate and had a number average molecular weight of 12,300; the polymer contained 18.3% water and was processed at 190°C; the solidification zone was maintained at 18 psig (1.24 bar), the first stage stretch was at a stretch ratio of 2.6 and the second stretch stage was a stretch ratio of 17 to provide a total stretch ratio of 46; and the resulting 3.9 d/f fiber was relaxed in steam at 124°C to provide a 5.1 d/f fiber. Physical properties are also given in Table I.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.4% acrylonitrile and 11.6% methyl methacrylate and had a number average molecular weight of 11,200; the polymer contained 18.6% water and was processed at 169°C; the solidification zone was maintained at 12 psig (0.83 bar), the first stage stretch was at a stretch ratio of 6.1 and the second stretch stage was at a stretch ratio of 7.2 to provide a total stretch ratio of 43.9; and the resulting 2.9 d/f fiber was relaxed in steam at 120°Cto provide a 4.1 d/ffiber. Physical properties are also given in Table I.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.6% acrylonitrile and 11.4% methyl methacrylate and had a number average molecular weight of 7,900; the polymer contained 13.1% water and was processed at 180°C; the solidification zone was maintained at 11 psig (0.76 bar), the first stretch stage was at a stretch ratio of 4.5 and the second stretch stage was at a stretch ratio of 7.1 to provide a total stretch ratio of 31.9; and the 3.0 d/f fiber was relaxed in steam at 120°C to provide a 4.3 d/ffiber. Physical properties are also given in Table I.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 88.4% acrylonitrile and 11.6% methyl methacrylate and had a number average molecular weight of 11,200; the polymer contained 13.5% water and was processed at 170°C; the solidification zone was maintained at 12 psig (0.83 bar), the first stretch stage was at a stretch ratio of 3.8 and the second stretch stage was at a stretch ratio of 12.2 to provide a total stretch ratio of 46.4; and the 3.2 d/f fiber was relaxed in steam at 125°C to provide a 5.0 d/ffiber. Physical properties are also given in Table I.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail with the following exceptions: the polymer contained 87.6% acrylonitrile, 11.9% methyl methacrylate and 0.5% 2-acrylamido-2-methylpropanesulfonic acid and had a number average molecular weight of 14,400; the polymer contained 15.5% water and was processed at 171°C; the solidification zone was maintained at 11 psig (0.76 bar), the first stretch stage was at a stretch ratio of 3.7 and the second stretch stage was at a stretch ratio of 10.7 to provide a total stretch ratio of 39.4; and the 2.2 d/f fiber was relaxed in steam at 125°C to provide at 3.4 d/f fiber. Physical properties are also given in Table I.
  • the fiber provided by Comparative Example B has considerably greater straight and loop tenacity values than the commercial acrylic fibers prepared by wet-spinning and dry-spinning procedures.
  • the fiber prepared by Examples 1 and 2 also have greater straight and loop properties than the commercial acrylic fibers.
  • the fibers prepared by Examples 3-6 all have properties within the ranges of values provided by commercial acrylic fibers in spite of the low molecular weight of the fiber-forming acrylonitrile polymers.
  • Comparative Example B The procedure of Comparative Example B was again followed in every material detail except for the acrylonitrile polymer employed.
  • a polymer containing 88.9% acrylonitrile and 11.1 % methyl methacrylate and having a number average molecular weight of 4,500 it was not possible to successfully spin a fusion melt of the polymer and water because an unsatisfactory fiber resulted. This indicates that an acrylonitrile polymer of this number average molecular weight value is unsuitable as a fiber-forming polymer.
  • the polymer contained 88.5% acrylonitrile and 11.5% methyl methacrylat.e and had a number average molecular weight of 5,300. Spinnability of a fusion melt with water of this polymer was marginal and proper processing to provide fiber for determination of physical properties could not be accomplished.
  • the minimum number average molecular weight of an acrylonitrile polymer for spinning as a fusion with water was about 6,000, preferably about 7,500.
  • Example 6 The procedure of Example 6 was again followed in every material detail except that the stretched fiber was dried for 23 minutes in an oven maintained at a dry bulb temperature of 138°C and a wet bulb temperature of 74°C. The dried fiber was then relaxed in steam to provide a shrinkage of 30%. The fiber obtained was tested in accordance with the following procedures.
  • a sample of fiber is dyed with Basic Blue 1 at 0.5 weight percent, based on the weight of fiber, to complete exhaustion.
  • the dyed sample is then dried in air at room temperature and a reflectance measurement is made versus a control using the Color-Eye at 620 millimicrons.
  • the control sample is a commercial wet spun acrylic fiber of the same denier dyed and handled in the same manner as the experimental fiber. The result is reported as the percent reflectance of that achieved by the control. In the case where the experimental fiber has more void structure than the control, there will be more light scattered and the dyed experimental fiber will register less than 100% reflectance at 620 millimicrons. The fiber will also appear to the eye to be lighter in color than the control.
  • a twenty gram sample of carded and scoured fiber is dyed with 0.5 weight percent of Basic Blue 1 based on the weight of fiber, at the boil until complete exhaustion occurs.
  • One portion of the dyed fiber is dried in air at room temperature.
  • Another portion is dried in an oven at 300°F (149°C), for 20 minutes. Reflectances of both samples are obtained using the Color-Eye at 620 millimicrons. The change in reflectance of the over-dried sample relative to the reflectance of the air dried sample is the shade change.
  • the dye intensity of the fiber obtained in Example 7 was 72 and the shade change was 13.
  • the fiber obtained in Example 6 which was not dried under conditions of controlled temperature and humidity prior to relaxation, was subjected to the same dye tests, the fiber exhibited a dye intensity of 40 and a shade change of 13.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
EP79301263A 1978-08-30 1979-06-29 Process for preparing acrylonitrile polymer fiber Expired EP0008849B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79301263T ATE928T1 (de) 1978-08-30 1979-06-29 Polyacrylnitrilfasern und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US938201 1978-08-30
US05/938,201 US4219523A (en) 1978-08-30 1978-08-30 Melt-spinning acrylonitrile polymer fiber from low molecular weight polymers

Publications (3)

Publication Number Publication Date
EP0008849A1 EP0008849A1 (en) 1980-03-19
EP0008849B1 EP0008849B1 (en) 1982-04-28
EP0008849B2 true EP0008849B2 (en) 1986-01-08

Family

ID=25471087

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79301263A Expired EP0008849B2 (en) 1978-08-30 1979-06-29 Process for preparing acrylonitrile polymer fiber

Country Status (22)

Country Link
US (1) US4219523A (fi)
EP (1) EP0008849B2 (fi)
JP (1) JPS5536391A (fi)
AR (1) AR217932A1 (fi)
AT (1) ATE928T1 (fi)
BR (1) BR7904642A (fi)
CA (1) CA1127815A (fi)
CS (1) CS252805B2 (fi)
DD (1) DD145642A5 (fi)
DE (1) DE2931439A1 (fi)
ES (1) ES483588A1 (fi)
GR (1) GR72262B (fi)
HU (1) HU178416B (fi)
IE (1) IE48680B1 (fi)
IN (1) IN152486B (fi)
MX (1) MX150675A (fi)
PH (1) PH15994A (fi)
PL (1) PL117369B1 (fi)
PT (1) PT69924A (fi)
RO (1) RO85024B1 (fi)
TR (1) TR21462A (fi)
YU (1) YU40375B (fi)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524105A (en) * 1977-11-17 1985-06-18 American Cyanamid Company Melt-spun acrylonitrile polymer fiber of improved properties
US4301107A (en) * 1978-08-30 1981-11-17 American Cyanamid Company Melt-spinning a plurality of acrylonitrile polymer fibers
DE2951803A1 (de) * 1979-12-21 1981-07-02 Bayer Ag, 5090 Leverkusen Feinsttitrige synthesefasern und -faeden und trockenspinnverfahren zu ihrer herstellung
US4278634A (en) * 1980-08-18 1981-07-14 American Cyanamid Company Biconstituent acrylic fibers by melt spinning
FR2489455B1 (fr) * 1980-09-04 1986-04-11 Valeo Garniture de friction, notamment pour freins, embrayages et autres applications
US4421707A (en) * 1982-04-29 1983-12-20 American Cyanamid Company Acrylic wet spinning process
US4515859A (en) * 1982-09-16 1985-05-07 American Cyanamid Company Hydrophilic, water-absorbing acrylonitrile polymer fiber
US4935180A (en) * 1988-08-25 1990-06-19 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers
US4981751A (en) * 1988-08-25 1991-01-01 Basf Aktiengesellschaft Melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers
US5168004A (en) * 1988-08-25 1992-12-01 Basf Aktiengesellschaft Melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers
US4921656A (en) * 1988-08-25 1990-05-01 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers
US4981752A (en) * 1989-07-06 1991-01-01 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers
US4933128A (en) * 1989-07-06 1990-06-12 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers
KR950005429B1 (ko) * 1991-03-27 1995-05-24 한국과학기술연구원 무방사 내열성 아크릴 단섬유

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2585444A (en) * 1948-07-29 1952-02-12 Du Pont Preparation of shaped articles from acrylonitrile polymers
US3984601A (en) * 1971-10-14 1976-10-05 E. I. Du Pont De Nemours And Company Acrylonitrile polymer filaments
US3896204A (en) * 1972-10-02 1975-07-22 Du Pont Melt-extrusion of acrylonitrile polymers into filaments
US4094948A (en) * 1972-10-02 1978-06-13 E. I. Du Pont De Nemours And Company Improved acrylonitrile polymer spinning process
IL43990A (en) * 1973-02-05 1976-08-31 American Cyanamid Co Method of spining fiber using a fusion-melt polymer composition
SE403141B (sv) * 1973-02-05 1978-07-31 American Cyanamid Co Smeltspinningsforfarande for framstellning av en akrylnitrilpolymerfiber
US3873508A (en) * 1973-12-27 1975-03-25 Du Pont Preparation of acrylonitrile polymer
US3991153A (en) * 1975-06-24 1976-11-09 American Cyanamid Company Single phase extrusion of acrylic polymer and water
GB1527004A (en) * 1976-11-01 1978-10-04 Japan Exlan Co Ltd Process for the melt-shaping of acrylonitrile polymers
US4205039A (en) * 1977-11-17 1980-05-27 American Cyanamid Company Process for melt-spinning acrylonitrile polymer fiber

Also Published As

Publication number Publication date
BR7904642A (pt) 1980-04-15
DE2931439A1 (de) 1980-03-20
EP0008849B1 (en) 1982-04-28
ES483588A1 (es) 1980-04-16
DD145642A5 (de) 1980-12-24
PT69924A (en) 1979-08-01
DE2931439C2 (fi) 1992-01-23
JPS6233327B2 (fi) 1987-07-20
PH15994A (en) 1983-05-20
PL218011A1 (fi) 1980-06-16
CS252805B2 (en) 1987-10-15
IE48680B1 (en) 1985-04-17
EP0008849A1 (en) 1980-03-19
YU40375B (en) 1985-12-31
IN152486B (fi) 1984-01-28
PL117369B1 (en) 1981-07-31
MX150675A (es) 1984-06-27
JPS5536391A (en) 1980-03-13
YU211879A (en) 1983-01-21
US4219523A (en) 1980-08-26
IE791650L (en) 1980-02-29
RO85024A2 (ro) 1984-08-17
CA1127815A (en) 1982-07-20
GR72262B (fi) 1983-10-10
CS588879A2 (en) 1987-03-12
RO85024B1 (ro) 1984-09-30
TR21462A (tr) 1984-06-18
HU178416B (en) 1982-05-28
ATE928T1 (de) 1982-05-15
AR217932A1 (es) 1980-04-30

Similar Documents

Publication Publication Date Title
EP0008849B2 (en) Process for preparing acrylonitrile polymer fiber
US3399259A (en) Method for producing bicomponent polypropylene filaments
US3655857A (en) Process for preparing acrylonitrile polymer solution
US3963790A (en) Non-inflammable filaments comprising acrylonitrile/vinylidene chloride copolymers
EP0103743B1 (en) Hydrophilic, water-absorbing acrylonitrile polymer fiber
EP0780498A1 (en) Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers
US4205039A (en) Process for melt-spinning acrylonitrile polymer fiber
US4301107A (en) Melt-spinning a plurality of acrylonitrile polymer fibers
US2842532A (en) Process of reducing the viscosity of polymers
US4524105A (en) Melt-spun acrylonitrile polymer fiber of improved properties
US4124673A (en) Process for the production of bifilar acrylic fibres
US5714101A (en) Process of making polyketon yarn
US4529768A (en) Solutions based on polyvinyl chloride, the process for their preparation and yarns and fibres thus obtained
US4447384A (en) Process for producing antipilling acrylic synthetic fiber
JPS62299513A (ja) ポリフエニレンサルフアイドモノフイラメントの製造方法
US2721785A (en) Acrylonitrile-styrene copolymer filaments and process of producing same
US5496510A (en) Acrylonitrile filament process
KR830000390B1 (ko) 저분자량 아크릴로니트릴 중합체로 부터 섬유제조방법
US4296175A (en) Hollow acrylonitrile polymer fiber
US3388031A (en) Crimped and crimpable vinylic filaments and fibers
Bajaj et al. Influence of spinning dope additives and spin bath temperature on the structure and physical properties of acrylic fibers
EP0014803A1 (en) Process for preparing acrylonitrile polymer fiber of hollow or open structure
US2953538A (en) Process of spinning acrylonitrile polymer solution in a mixture of solvents
US3382307A (en) Process for the stretching of polyamidic fibres
US4379113A (en) Melt spinning process for acrylonitrile polymer fiber-three or more stretch stages

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE FR GB IT LU NL SE

17P Request for examination filed
ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE FR GB IT LU NL SE

REF Corresponds to:

Ref document number: 928

Country of ref document: AT

Date of ref document: 19820515

Kind code of ref document: T

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HOECHST AKTIENGESELLSCHAFT, FRANKFURT

Effective date: 19830126

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19830519

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19840629

RTI2 Title (correction)

Free format text: PROCESS FOR PREPARING ACRYLONITRILE POLYMER FIBER.

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form
AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE FR GB IT LU NL SE

ET3 Fr: translation filed ** decision concerning opposition
NLR2 Nl: decision of opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
ITF It: translation for a ep patent filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19910410

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910524

Year of fee payment: 13

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910630

Year of fee payment: 13

EPTA Lu: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920505

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19920630

BERE Be: lapsed

Owner name: AMERICAN CYANAMID CY

Effective date: 19920630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930630

EUG Se: european patent has lapsed

Ref document number: 79301263.4

Effective date: 19940110

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960509

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960607

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970629

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST